U.S. patent application number 11/175545 was filed with the patent office on 2006-03-09 for hydrocarbon extenders for surface effect compositions.
Invention is credited to Patrick Henry Fitzgerald, Justine Gabrielle Franchina.
Application Number | 20060052556 11/175545 |
Document ID | / |
Family ID | 35509318 |
Filed Date | 2006-03-09 |
United States Patent
Application |
20060052556 |
Kind Code |
A1 |
Franchina; Justine Gabrielle ;
et al. |
March 9, 2006 |
Hydrocarbon extenders for surface effect compositions
Abstract
A polymer extender composition for use with fluorochemical
repellents, said composition comprising monomers copolymerized in
the following percentages by weight: (a) from about 60% to about
94% of a monomer, or mixture of monomers, of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I), and (b) from about 5% to about 20% of a
monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II)
wherein each R is independently H or CH.sub.3; n is 1 to 10; p is 1
to 20 and m is 2 to 10 is disclosed.
Inventors: |
Franchina; Justine Gabrielle;
(Hockessin, DE) ; Fitzgerald; Patrick Henry;
(Hockessin, DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY;LEGAL PATENT RECORDS CENTER
BARLEY MILL PLAZA 25/1128
4417 LANCASTER PIKE
WILMINGTON
DE
19805
US
|
Family ID: |
35509318 |
Appl. No.: |
11/175545 |
Filed: |
July 6, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60607612 |
Sep 7, 2004 |
|
|
|
Current U.S.
Class: |
526/242 ;
526/319 |
Current CPC
Class: |
C14C 9/00 20130101; D06M
15/27 20130101; D06M 15/277 20130101; D21H 19/20 20130101; C08G
18/6266 20130101; D06M 15/263 20130101; C08G 18/80 20130101; D06M
15/29 20130101 |
Class at
Publication: |
526/242 ;
526/319 |
International
Class: |
C08F 14/18 20060101
C08F014/18 |
Claims
1. A polymer extender composition comprising monomers copolymerized
in the following percentages by weight: (a) from about 60% to about
94% of a monomer, or mixture of monomers, of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I), and (b) from about 5% to about 20% of a
monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II) (c)
from about 0% to about 3% of a monomer, or mixture of monomers, of
the formula III: HO--CH.sub.2--NH--C(O)--C(R).dbd.CH.sub.2 (III)
(d) from about 0% to about 20% of a monomer, or mixture of
monomers, of formula IV: R.sup.1--OC(O)--C(R).dbd.CH.sub.2 (IV) (e)
from about 0% to about 2% of ethylene dimethacrylate, and (f) from
about 0% to about 10% of a monomer, or mixture of monomers, of
formula (V): R.sub.f--CH.sub.2CH.sub.2--OC(O)--C(R).dbd.CH.sub.2
(V) wherein each R is independently H or CH.sub.3; R.sup.1 is an
alkyl chain from 1 to about 18 carbon atoms; n is 1 to about 10; p
is 1 to about 20 and m is 2 to about 10, and R.sub.f is a straight
or branched-chain perfluoroalkyl group of from 2 to about 20 carbon
atoms, or a mixture thereof.
2. The composition of claim 1 wherein monomer (a) is
2-ethylhexyl(meth)acrylate.
3. The composition of claim 1 wherein m in monomer (b) is between
about 5 and about 10.
4. The composition of claim 1 wherein monomer (c) is
N-methylolacrylamide.
5. The composition of claim 1 wherein monomer (d) is methyl
methacrylate.
6. The composition of claim 1 wherein for monomer (f), R.sub.f has
the formula: CF.sub.3CF.sub.2(CF.sub.2).sub.x, wherein x is 6 to
18, or a mixture thereof.
7. The composition of claim 6 wherein x is a mixture of 6, 8, 10,
12, 14, 16, and 18 in a mixture in the respective relative amounts
of about 33%, 24%, 12%, 6%, 2%, 1% and 0.5%.
8. The composition of claim 1 as an aqueous dispersion.
9. The composition of claim 1 further comprising an agent which,
when applied to a substrate, provides a surface effect.
10. The composition of claim 9 wherein the surface effect is no
iron, easy to iron, shrinkage control, wrinkle free, permanent
press, moisture control, softness, strength, anti-slip,
anti-static, anti-snag, anti-pill, stain repellency, stain release,
soil repellency, soil release, water repellency, oil repellency,
odor control, antimicrobial, sun protection, and similar
effects.
11. The composition of claim 9 wherein the agent is a fluorinated
polymer.
12. The composition of claim 11 wherein the fluorine content is
from about 1.5 to about 6.6% by weight.
13. The composition of claim 11 wherein the ratio of extender
composition to fluorinated polymer is from about 1:10 to about
6:1.
14. The composition of claim 11 wherein the fluorinated polymer is
a fluorine-containing polyurethane or poly(meth)acrylate, or
mixture thereof.
15. The composition of claim 1 or 11 further comprising a blocked
isocyanate.
16. The composition of claim 1 or 11 further comprising at least
one additional extender.
17. The composition of claim 9 further comprising an additive
selected from the group consisting of a surfactant, emulsifier, pH
adjuster, cross linker, wetting agent, softener, and wax
extender.
18. A method of treating a substrate comprising contacting the
substrate with a composition comprising i) an agent which provides
a surface effect and ii) a polymer extender composition comprising
monomers copolymerized in the following percentages by weight: (a)
from about 60% to about 94% of a monomer, or mixture of monomers,
of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I), and (b) from about 5% to about 20% of a
monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II) (c)
from about 0% to about 3% of a monomer, or mixture of monomers, of
the formula III: HO--CH.sub.2--NH--C(O)--C(R).dbd.CH.sub.2 (III)
(d) from about 0% to about 20% of a monomer, or mixture of
monomers, of formula IV: R.sup.1--OC(O)--C(R).dbd.CH.sub.2 (IV) (e)
from about 0% to about 2% of ethylene dimethacrylate, and (f) from
about 0% to about 10% of a monomer, or mixture of monomers, of
formula (V): R.sub.f--CH.sub.2CH.sub.2--OC(O)--C(R).dbd.CH.sub.2
(V) wherein each R is independently H or CH.sub.3; R.sup.1 is an
alkyl chain from 1 to about 18 carbon atoms; n is 1 to about 10; p
is 1 to about 20 and m is 2 to about 10, and R.sub.f is a straight
or branched-chain perfluoroalkyl group of from 2 to about 20 carbon
atoms, or a mixture thereof.
19. The method of claim 18 wherein the surface effect is no iron,
easy to iron, shrinkage control, wrinkle free, permanent press,
moisture control, softness, strength, anti-slip, anti-static,
anti-snag, anti-pill, stain repellency, stain release, soil
repellency, soil release, water repellency, oil repellency, odor
control, antimicrobial, sun protection, and similar effects.
20. The method of claim 18 wherein the agent is a fluorinated
polymer.
21. The method of claim 20 wherein the ratio of the extender
composition to the fluorinated polymer is from about 1:10 to about
6:1.
22. The method of claim 18 wherein the composition further
comprises a blocked isocyanate or at least one additional
extender.
23. The method of claim 18 wherein the composition further
comprises an additive selected from the group consisting of a
surfactant, emulsifier, pH adjuster, cross linker, wetting agent,
softener, and wax extender.
24. The method of claim 18 wherein the substrate is a fiber,
textile, fabric, fabric blend, paper, nonwoven, leather or
combination thereof.
25. A substrate treated by the method of claim 18.
26. A substrate treated by a composition comprising i) an agent
which provides a surface effect and ii) a polymer extender
composition comprising monomers copolymerized in the following
percentages by weight: (a) from about 60% to about 94% of a
monomer, or mixture of monomers, of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I), and (b) from about 5% to about 20% of a
monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II) (c)
from about 0% to about 3% of a monomer, or mixture of monomers, of
the formula III: HO--CH.sub.2--NH--C(O)--C(R).dbd.CH.sub.2 (III)
(d) from about 0% to about 20% of a monomer, or mixture of
monomers, of formula IV: R.sup.1--OC(O)--C(R).dbd.CH.sub.2 (IV) (e)
from about 0% to about 2% of ethylene dimethacrylate, and (f) from
about 0% to about 10% of a monomer, or mixture of monomers, of
formula (V): R.sub.f--CH.sub.2CH.sub.2--OC(O)--C(R).dbd.C H.sub.2
(V) wherein each R is independently H or CH.sub.3; R.sup.1 is an
alkyl chain from 1 to about 18 carbon atoms; n is 1 to about 10; p
is 1 to about 20 and m is 2 to about 10, and R.sub.f is a straight
or branched-chain perfluoroalkyl group of from 2 to about 20 carbon
atoms, or a mixture thereof.
27. A substrate of claim 26 wherein the surface effect is no iron,
easy to iron, shrinkage control, wrinkle free, permanent press,
moisture control, softness, strength, anti-slip, anti-static,
anti-snag, anti-pill, stain repellency, stain release, soil
repellency, soil release, water repellency, oil repellency, odor
control, antimicrobial, sun protection, and similar effects.
28. A substrate of claim 26 wherein the agent is a fluorinated
polymer.
29. A substrate of claim 26 wherein the composition further
comprises a blocked isocyanate.
30. A substrate of claim 26 wherein the composition further
comprises an additive selected from the group consisting of a
surfactant, emulsifier, pH adjuster, cross linker, wetting agent,
softener, and wax extender.
31. A substrate of claim 26 which is a fiber, textile, fabric,
fabric blend, paper, nonwoven, leather, or combination thereof.
32. The substrate of claim 26 having a fluorine content of from
about 0.05% to about 0.5% by weight.
Description
FIELD OF THE INVENTION
[0001] Hydrocarbon polymers are employed as extenders to improve
the performance of treating agents which provide surface effects to
treated substrates.
BACKGROUND OF THE INVENTION
[0002] Various compositions are known to be useful as treating
agents to provide surface effects to substrates. Surface effects
include repellency to moisture, soil and stain resistance, and
other effects which are particularly useful for fibrous substrates
such as fibers, fabrics, textiles, carpets, paper, leather and
other such substrates. Many such treating agents are fluorinated
polymers or copolymers.
[0003] Fluorinated polymer compositions having utility as fibrous
substrate treating agents generally contain pendant perfluoroalkyl
groups of three or more carbon atoms, which provide oil- and
water-repellency when the compositions are applied to fibrous
substrate surfaces. The perfluoroalkyl groups are generally
attached by various connecting groups to polymerizable groups not
containing fluorine. The resulting monomer is then generally
copolymerized with other monomers which confer additional favorable
properties to the substrates. Various specialized monomers may be
incorporated to impart improved cross-linking, latex stability and
substantivity. Since each ingredient may impart some potentially
undesirable properties in addition to its desirable ones, the
specific combination is directed to the desired use. These polymers
are generally marketed as aqueous emulsions for easy application to
the fibrous substrates.
[0004] Various attempts have been made to increase the oil- and
water-repellency imparted to the substrate and its durability while
reducing the amount of fluorinated polymer required, i.e., boost
the efficiency or performance of the treating agent. One method is
to incorporate blocked isocyanates or melamine resins. However,
only limited amounts can be used because these ingredients tend to
adversely affect the handle (the feel) of the fibrous substrate.
Another method is the use of various extender polymers. These are
typically hydrocarbon polymers in aqueous emulsions, which are
blended with the fluorinated polymer emulsion before application to
the substrate.
[0005] U.S. Pat. No. 3,657,173 discloses an emulsion suitable for
imparting oil and/or water-repellency to substrates, containing a
fluorinated polymer and a major amount of a halogenated solvent, a
minor amount of an alkanol, and water. Optionally the emulsion may
also contain a non-fluorine containing polymer, (i.e., an extender
polymer), of at least one monovinyl compound free of non-vinylic
fluorine atoms, or a non-fluorinated conjugated diene. Examples of
the extender polymer are 2-hydroxy ethyl- or 2-hydroxy
propyl-acrylate or methacrylate; and n-lauryl methacrylate or
2-ethylhexyl methacrylate. It is also said to be advantageous to
include in all these polymers a small amount of units derived from
N-methylolacrylamide or N-methylolmethacrylamide and glycidyl
acrylate or methacrylate to improve durability of the polymer
solids to laundering or dry-cleaning.
[0006] There is a need for polymer compositions which significantly
improve the performance of surface effect agents. In particular,
there is a need for compositions which improve the durability of
surface effects for substrates while reducing the amount of
fluorinated polymer required. The present invention provides such a
composition.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention comprises a polymer composition for
use with treating agents providing a surface effect to substrates,
comprising monomers copolymerized in the following percentages by
weight: [0008] (a) from about 60% to about 94% of a monomer, or
mixture of monomers, of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I), and [0009] (b) from about 5% to about 20% of
a monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II)
[0010] (c) from about 0% to about 3% of a monomer, or mixture of
monomers, of the formula III:
HO--CH.sub.2--NH--C(O)--C(R).dbd.CH.sub.2 (III) [0011] (d) from
about 0% to about 20% of a monomer, or mixture of monomers, of
formula IV: R.sup.1--OC(O)--C(R).dbd.CH.sub.2 (IV) [0012] (e) from
about 0% to about 2% of ethylene dimethacrylate, and [0013] (f)
from about 0% to about 10% of a monomer, or mixture of monomers, of
formula (V): R.sub.f--CH.sub.2CH.sub.2--OC(O)--C(R).dbd.C H.sub.2
(V). [0014] wherein [0015] each R is independently H or CH.sub.3;
[0016] R.sup.1 is an alkyl chain from 1 to about 18 carbon atoms;
[0017] n is 1 to about 10; [0018] p is 1 to about 20 and [0019] m
is 2 to about 10, and [0020] R.sub.f is a straight or
branched-chain perfluoroalkyl group of from 2 to about 20 carbon
atoms, or a mixture thereof.
[0021] The present invention further comprises a method of treating
a substrate comprising contacting said substrate with a composition
comprising a treating agent which when applied to a substrate
provides a surface effect and the above-described composition.
[0022] The present invention further comprises a substrate treated
with a composition comprising a treating agent which when applied
to a substrate provides a surface effect and the above-described
composition.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Trademarks are indicated herein by capitalization.
[0024] This invention comprises a polymer composition useful for
improving the durability performance of treating agents which
provide surface effects to substrates. In particular, the extender
composition is useful for improving the performance of fluorinated
polymers in imparting durable repellent properties to fibrous
substrates. The fibrous substrates include fibers, textiles, paper,
nonwovens, leather, carpets, fabrics, fabric blends or a
combination thereof. By "fabrics" is meant natural or synthetic
fabrics, or blends thereof, composed of fibers such as cotton,
rayon, silk, wool, polyester, polypropylene, polyolefins, nylon,
and aramids such as "NOMEX" and "KEVLAR." By "fabric blends" is
meant fabric made of two or more types of fibers. Typically these
blends are a combination of at least one natural fiber and at least
one synthetic fiber, but also can be a blend of two or more natural
fibers or of two or more synthetic fibers.
[0025] Superior durable surface properties, along with desirable
properties of low yellowing and good durability, are imparted to
fibrous substrates by the addition of the inventive extender
polymer composition to surface treating agents before application
to fibrous substrates. These combined blends are applied to the
fibrous substrates in the form of a dispersion in water or other
solvent either before, after or during the application of other
treatment chemicals.
[0026] When so applied, the extender composition of this invention
in combination with a fluorinated polymer treating agent has been
found in particular to improve the durability of surface
properties, especially oil- and water-repellency, in fibrous
substrates after laundering by as much as 50%. The durability of
the repellency is improved compared to other known extender
compositions. Further, use of the extender composition of the
present invention increases fluorine efficiency by permitting use
of lower levels of the fluorinated polymer.
[0027] The extender polymer compositions of this invention are
prepared by conventional emulsion polymerization techniques, such
as those used to make fluorinated polymers. Generally, such
copolymers are prepared by copolymerization of two or more monomers
in an aqueous media with the resulting dispersion or emulsion
stabilized with a surfactant. Optionally, the copolymerization is
carried out by solution polymerization, wherein an organic
water-soluble solvent, such as alcohol or glycol, is added to the
aqueous media to improve the solubility of the monomers. The
surfactant employed to stabilize the emulsion during its formation
and during polymerization can be a conventional anionic, cationic
and/or nonionic emulsifying agent or agents. The polymerization is
conveniently initiated by azo initiators such as
2,2'-azobis(2-amidinopropane) dihydrochloride. These initiators are
sold by E. I. du Pont de Nemours and Company, Wilmington, Del.,
commercially under the name of "VAZO".
[0028] The aqueous dispersion blends produced by mixing the
extender composition dispersion with a fluorinated polymer
dispersion are applied to surfaces of fibrous substrates by known
methods to impart oil-, soil- and water-repellency and other
surface effects. A distinguishing feature of use of the fluorinated
polymer-extender compositions of the present invention is high
durability of the repellent finish on the fabric.
[0029] The composition of the present invention comprises a
copolymer comprising monomers copolymerized in the following
percentages by weight: [0030] (a) from about 60% to about 94% of a
monomer, or mixture of monomers, of the formula I:
[CH.sub.3--(CH.sub.2).sub.p][CH.sub.3(CH.sub.2).sub.n]CHCH.sub.2--OC(O)---
C(R).dbd.CH.sub.2 (I) [0031] (b) from about 5% to about 20% of a
monomer, or mixture of monomers, of the formula II:
H--(OCH.sub.2CH.sub.2).sub.m--O--C(O)--C(R).dbd.CH.sub.2 (II)
[0032] (c) from about 0% to about 3% of a monomer, or mixture of
monomers, of the formula III:
HO--CH.sub.2--NH--C(O)--C(R).dbd.CH.sub.2 (III) [0033] (d) from
about 0% to about 20% of a monomer, or mixture of monomers, of
formula IV: R.sup.1--OC(O)--C(R).dbd.CH.sub.2 (IV) [0034] (e) from
about 0% to about 2% of ethylene dimethacrylate, and [0035] (f)
from about 0% to about 10% of a monomer, or mixture of monomers, of
formula (V): R.sub.f--CH.sub.2CH.sub.2--OC(O)--C(R).dbd.CH.sub.2
(V) [0036] wherein [0037] each R is independently H or CH.sub.3;
[0038] R.sup.1 is an alkyl chain from 1 to about 18 carbon atoms;
[0039] n is 1 to about 10; [0040] p is 1 to about 20 and m is 2 to
about 10, and [0041] R.sub.f is a straight or branched-chain
perfluoroalkyl group of from 2 to about 20 carbon atoms, or a
mixture thereof.
[0042] The term "(meth)acrylate" is used herein to mean either
methacrylate, acrylate or a mixture of the two.
[0043] The required monomer (a) of formula I in the present
invention is one or a mixture of branched-chain
alkyl(meth)acrylates having about 6 to about 34 carbon atoms in its
alkyl chain. It is added to the polymerization in proportions from
about 60% to about 94% by weight. Preferably the proportion of
monomer (a) in the copolymer is between about 70 % and about 90% by
weight. Preferably the branched-chain (meth)acrylate is
2-ethylhexyl(meth)acrylate.
[0044] The required monomer (b) of formula III in the present
invention is one or a mixture of ethoxylated (meth)acrylates
wherein the number of ethoxy groups is between 2 and about 10.
Between about 5 and about 10 ethoxy groups are preferred. It is
added to the polymerization in proportions from about 5% to about
20% by weight. Preferably the proportion of monomer (b) in the
extender copolymer is between about 8% and about 15% by weight.
[0045] The optional monomer (c) of formula III in the present
invention is N-methylol acrylamide, N-methylol methacrylamide or a
mixture of the two. N-methylol acrylamide is preferred. It is added
to the polymerization in proportions of 0% to about 3%. About 1% by
weight is preferred. This monomer is typically employed to help
improve durability of the repellency properties imparted to the
treated substrate.
[0046] Optional monomer (d) of formula IV is a linear alkyl chain
(meth)acrylate wherein the alkyl chain has between 1 and about 18
carbon atoms. Methyl methacrylate is preferred. It is added to the
polymerization in proportions from 0 to about 20% by weight. About
12% by weight is preferred.
[0047] Optional monomer (e) is ethylene dimethacrylate,
[CH.sub.2CH(CH.sub.3)C(O)CH.sub.2CH.sub.2].sub.2. It is added to
the polymerization in proportions from 0 to about 2%. About 0.5% by
weight is preferred. Inclusion of monomers (d) and (e) provides
flexibility to adapt to various specific substrates while
maintaining effective performance.
[0048] Optional monomer (f) of formula V is a
perfluoro(meth)acrylate with a straight or branched-chain
perfluoroalkyl group of from about 2 to about 20 carbon atoms or a
mixture thereof. Preferably, the perfluoroalkyl group
CF.sub.3CF.sub.2(CF.sub.2).sub.x-- has from about 6 to about 18
carbon atoms, or a mixture thereof. A perfluoro(meth)acrylate is
preferred of the formula:
CF.sub.3CF.sub.2(CF.sub.2).sub.xC.sub.2H.sub.4OC(O)--C(CH.sub.3).dbd.CH.s-
ub.2, wherein x is 6, 8, 10, 12, 14, 16, and 18 in a mixture in the
respective relative amounts of about 33%, 24%, 12%, 6%, 2%, 1% and
0.5%, and said monomer has a weight average molecular weight of
about 583. It is added to the polymerization in proportions from
about 0 to about 10%, with 0% being preferred. The presence of this
monomer may enhance compatibility in the blend with the
fluorochemical treatment agent.
[0049] The copolymer dispersions described above are then blended
with any of a variety of known treating agents for fibrous
substrates. Examples of fluorinated polymer treating agents are
ZONYL available from E. I. du Pont de Nemours and Company,
Wilmington, Del.; OLEOPHOBOL from Ciba Specialty Chemicals,
Langweid, Germany; ASAHI GARD from Asahi Glass Company, Ltd.,
Tokyo, Japan; UNIDYNE from Daikin America, Inc., Orangeburg, N.Y.;
SCOTCHGARD from 3M Company, St. Paul, Minn.; and NANO TEX from
Nanotex, Emeryville, Calif. Of particular interest are fluorinated
polymers useful as treating agents to provide repellency properties
to the surface of treated substrates. The copolymer dispersion is
blended with the fluorinated polymer in a ratio of from about 1:10
to about 6:1, preferably from about 1:3 to about 3:1, and more
preferably from about 2:1 to about 1:2. The fluorine content of the
blend is from about 1.5% to about 6.6% by weight, preferably from
about 2.0% to about 4.0% by weight. The fluorinated polymer
treating agents are any of those used for creating water or oil
repellency on a fibrous substrate. These include fluorochemical
compounds or polymers containing one or more fluoroaliphatic groups
(designated here as R.sub.f groups) which are fluorinated, stable,
inert, non-polar, preferably saturated, monovalent and both
oleophobic and hydrophobic. The R.sub.f groups preferably contain
at least 3 carbon atoms, more preferably 3 to 20 carbon atoms, and
most preferably about 6 to about 14 carbon atoms. The R.sub.f
groups may contain straight or branched chain or cyclic fluorinated
alkylene groups or combinations thereof. The terminal portion of
the R.sub.f groups is a perfluorinated aliphatic group of the
formula C.sub.nF.sub.2n+1 wherein n is from about 3 to about
20.
[0050] Examples of such fluorinated polymers preferably include
R.sub.f-containing polyurethanes and poly(meth)acrylates.
Especially preferred are copolymers of fluorochemical
(meth)acrylate monomers with a co-polymerizable monovinyl compound
or a conjugated diene. The co-polymerizable monovinyl compounds
include alkyl(meth)acrylates, vinyl esters of aliphatic acids,
styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl
esters, vinyl alkyl ketones, and acrylamides. The conjugated dienes
are preferably 1,3-butadienes. Representative compounds within the
preceding classes include the methyl, propyl, butyl,
2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl,
decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates;
vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate,
vinyl stearate, styrene, alpha methyl styrene, p-methylstyene,
vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride,
vinylidene chloride, allyl heptanoate, allyl acetate, allyl
caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone,
1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene,
isoprene, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl
acrylate, glycidyl methacrylate, and polyoxymethacrylates.
[0051] The blended composition comprising a fluorinated polymer and
the extender polymer of the present invention applied to the
fibrous substrate optionally further comprises a blocked isocyanate
to promote durability, added after copolymerization (i.e., as a
blended isocyanate). An example of a suitable blocked isocyanate is
HYDROPHOBOL XAN available from Ciba Specialty Chemicals, High
Point, N.J. Other commercially available blocked isocyanates are
also suitable for use herein. The desirability of adding a blocked
isocyanate depends on the particular application for the copolymer.
For most of the presently envisioned applications, it does not need
to be present to achieve satisfactory cross-linking between chains
or bonding to the fibers. When added as a blended isocyanate,
amounts up to about 20% by weight are added.
[0052] The blended composition comprising a fluorinated polymer and
the extender composition of the present invention optionally
further comprises additional components such as treating agents or
finishes to achieve additional surface effects, or additives
commonly used with such agents or finishes. Such additional
components comprise compounds or compositions that provide surface
effects such as no iron, easy to iron, shrinkage control, wrinkle
free, permanent press, moisture control, softness, strength,
anti-slip, anti-static, anti-snag, anti-pill, stain repellency,
stain release, soil repellency, soil release, water repellency, oil
repellency, odor control, antimicrobial, sun protection, and
similar effects. One or more such treating agents or finishes can
be combined with the blended composition and applied to the fibrous
substrate. Other additives commonly used with such treating agents
or finishes may also be present such as surfactants, pH adjusters,
cross linkers, wetting agents, wax extenders, and other additives
known by those skilled in the art. Further, other extender
compositions are optionally included to obtain a combination of
benefits.
[0053] The present invention further comprises a method of treating
substrates comprising contacting the surface of the substrate with
an effective amount of a composition comprising an extender
composition of the present invention as described above and a
treating agent which provides a surface effect when applied to a
substrate. Preferably, the treating agent is a fluorinated polymer.
The blended compositions are applied to the fibrous substrate to be
treated from aqueous dispersions, either alone or in a mixture with
other textile treatment agents, finishes or additives as described
above. For example, when synthetic fabrics are treated, a wetting
agent can be used, such as ALKANOL 6112 available from E. I. du
Pont de Nemours and Company, Wilmington, Del. As a further example,
when cotton or cotton-blended fabrics are treated, a
wrinkle-resistant resin can be used such as PERMAFRESH EFC
available from Omnova Solutions, Chester, S.C. As a further
example, when nonwoven fabrics are treated, a wax extender can be
employed such as FREEPEL 1225WR, available from Omnova Solutions
Chester, S.C. An antistat such as ZELEC KC, available from Stepan,
Northfield, Ill., or a wetting agent, such as hexanol, also are
suitable. The dispersions are generally applied to fibrous
substrates by spraying, dipping, padding, or other well-known
methods. After excess liquid has been removed, for example by
squeeze rolls, the treated fibrous substrate is dried and then
cured by heating, for example, to from about 100.degree. C. to
about 190.degree. C., for at least 30 seconds, typically from about
60 to about 240 seconds. Such curing enhances oil-, water- and soil
repellency and durability of the repellency. While these curing
conditions are typical, some commercial apparatus may operate
outside these ranges because of its specific design features. The
treated fibrous substrate has a fluorine content of from about
0.05% to about 0.5% by weight.
[0054] The present invention further comprises substrates treated
with the above-described composition comprising i) a treating agent
which provides a surface effect and ii) the extender copolymer of
the present invention as described above. The composition also can
contain optional agents to provide additional surface effects as
described above, optional additives commonly used in treating
substrates as described above, optional blocked isocyanate as
described above, and optional additional distinct extender
compositions. As previously noted such substrates include paper,
nonwovens, leather, fibers, textiles, fabrics, fabric blends, or
combinations thereof. "Fabrics" includes natural or synthetic
fabrics composed of fibers of cotton, rayon, silk, wool, polyester,
polypropylene, polyolefins, nylon, and aramids such as "NOMEX" and
"KEVLAR." By "fabric blends" is meant fabric made of two or more
types of fibers. Typically these blends are a combination of at
least one natural fiber and at least one synthetic fiber, but also
can be a blend of two or more natural fibers or of two or more
synthetic fibers. Preferably, the substrate has been treated with a
composition comprising an extender composition of the present
invention and a fluorinated polymer such as a polyurethane or
poly(meth)acrylate.
[0055] Specifically, the copolymer compositions, method and treated
substrates of the present invention are useful to enhance surface
properties, especially durability of oil-, water- and
soil-repellency, of the above-described substrates while reducing
the amount of fluorinated polymer employed. The repellency property
is more durable than applications of fluorinated polymer treating
agents with other extenders, and is effective for various fibrous
substrates. The repellency property is effective with a variety of
other surface effects. The treated fibrous substrates of the
present invention are useful in a variety of applications such as
for textiles, clothing, uniforms, protective garments, furnishings,
and the like. The copolymers of the present invention are
advantageous in that when blended with fluorinated polymer treating
agents, they give highly durable, low yellowing repellent finishes
over a wide range of fibrous substrates while using a reduced level
of the fluorinated polymer. The inventive compositions are made at
lower materials cost than the currently available acrylate
copolymers.
Test Methods
[0056] The following tests were employed in evaluating the examples
herein.
Test Method 1--Fabric Treatment
[0057] The fabric was treated with the copolymer blend using a
conventional pad bath (dipping) process. A bath containing 0.2-5%
by weight of the fluorinated polymer treating agent blended with
the extender copolymer of the present invention (hereinafter
copolymer blend), as detailed in the Tables in the Example section,
was used to treat fabrics, such as cotton, nonwoven, and nylon
fabrics, in combination with a blocked isocyanate (0-2%) as
indicated. A bath containing 30-45 g/L of the copolymer blend was
used. The fluorochemicals used for blending with the nonfluorinated
copolymer extenders of the present invention were commercial ZONYL
products that are available from E. I. du Pont de Nemours and
Company, Wilmington, Del. After application, the woven fabrics were
cured at approximately 160 .degree. C. for 1-3 minutes, and the
nonwoven fabrics were cured at 100-170.degree. C. for 2-4 minutes.
The fabric was allowed to "rest" after treatment and cure.
Test Method 2--Water Repellency
[0058] The water repellency of a treated substrate was measured
according to the DuPont Technical Laboratory Method as outlined in
the TEFLON.RTM. Global Specifications and Quality Control Tests
information packet or AATCC standard Test Method No. 193-2004. The
test determines the resistance of a treated substrate to wetting by
aqueous liquids. Drops of water-alcohol mixtures of varying surface
tensions are placed on the fabric and the extent of surface wetting
is determined visually. The test provides a rough index of aqueous
stain resistance. The higher the water repellency rating, the
better the resistance of a finished substrate to staining by
water-based substances. The composition of standard test liquids is
shown in the following table. TABLE-US-00001 TABLE 1 Standard Test
Liquids Water Repellency Composition, Vol % Rating Number Isopropyl
Alcohol Distilled Water 1 2 98 2 5 95 3 10 90 4 20 80 5 30 70 6 40
60 7 50 50 8 60 40 9 70 30 10 80 20 11 90 10 12 100 0
Test Method 3--Water Repellency--Spray Rating
[0059] Water repellency can be further tested by utilizing the
spray test method. The treated fabric samples were tested for water
repellency by following the AATCC standard Test Method No. 22-1996,
conducted as follows. A fabric sample, treated with an aqueous
dispersion of polymer as previously described, is conditioned for a
minimum of 2 hours at 23.degree. C.+20% relative humidity and
65.degree. C.+10% relative humidity. The fabric sample is securely
fastened on a plastic/metal embroidery hoop such that the fabric is
wrinkle-free. The hoop is placed on the testing stand so that the
fabric is facing up. Then 250 mL of water at 80.+-.2.degree. F.
(27.+-.1.degree. C.) is poured into the testing funnel allowing the
water to spray onto the fabric surface. Once the water has run
through the funnel, the hoop is rapped against the edge of a solid
object with the fabric facing down, rotated 180 degrees and rapped
again. The spotted or wetted surface is compared with the AATCC
standards found in the AATCC Technical Manual. The more wet the
surface, the lower the number and the poorer the repellency. A 100
denotes no wetting, a 90 denotes slight wetting (three small
spots), an 80 denotes wetting signified by several (10) spots at
the spray points, a 70 denotes partial wetting of the upper fabric
surface, a 50 denotes wetting of the entire upper fabric surface,
and a 0 denotes complete wetting of the lower and upper fabric
surface.
Test Method 4--Oil Repellency
[0060] The treated fabric samples were tested for oil repellency by
a modification of AATCC standard Test Method No. 118, conducted as
follows. A fabric sample, treated with an aqueous dispersion of
polymer as previously described, is conditioned for a minimum of 2
hours at 23.degree. C.+20% relative humidity and 65.degree. C.+10%
relative humidity. A series of organic liquids, identified below in
Table I, are then applied drop wise to the fabric samples.
Beginning with the lowest numbered test liquid (Repellency Rating
No. 1), one drop (approximately 5 mm in diameter or 0.05 mL volume)
is placed on each of three locations at least 5 mm apart. The drops
are observed for 30 seconds. If, at the end of this period, two of
the three drops are still spherical in shape with no wicking around
the drops, three drops of the next highest numbered liquid are
placed on adjacent sites and similarly observed for 30 seconds. The
procedure is continued until one of the test liquids results in two
of the three drops failing to remain spherical to hemispherical, or
wetting or wicking occurs.
[0061] The oil repellency rating of the fabric is the highest
numbered test liquid for which two of the three drops remained
spherical to hemispherical, with no wicking for 30 seconds. In
general, treated fabrics with a rating of 6 or more are considered
good to excellent; fabrics having a rating of one or greater can be
used in certain applications. TABLE-US-00002 TABLE 2 Oil Repellency
Test Liquids Oil Repellency Rating Number Test Solution 1 NUJOL
Purified Mineral Oil 2 65/35 NUJOL/n-hexadecane by volume at
21.degree. C. 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6
n-decane 7 n-octane 8 n-heptane Note: NUJOL is a trademark of
Plough, Inc., for a mineral oil having a Saybolt viscosity of
360/390 at 38.degree. C. and a specific gravity of 0.880/0.900 at
15.degree. C.
Test Method5--Impact Repellency Procedure
[0062] Water resistance can be further tested by utilizing the
impact test method. The treated fabric samples were tested for
water repellency by following the AATCC standard Test Method No.
42-2000, conducted as follows. A fabric sample, treated with an
aqueous dispersion of copolymer blend as previously described, is
conditioned for a minimum of 2 hours at 23.degree. C. plus 20%
relative humidity and 65.degree. C. plus 10% relative humidity. The
fabric sample is securely fastened on flat surface, that sits at a
45-degree angle, such that the fabric is wrinkle-free. A piece of
blotter paper, the same size that the fabric, is placed behind the
fabric. Then 500 mL of water at 82.+-.2.degree. F. (27.+-.1.degree.
C.) is poured into the testing funnel allowing the water to spray
onto the fabric surface. Once the water has run through the funnel,
the blotter paper is weighed. An increase in weight that is less
than a half a gram is considered very good.
Test Method 6--Laundering Procedure
[0063] The fabric samples were laundered according to the U.S. Home
Laundering Method outlined in the TEFLON Global Specifications and
Quality Control Tests information packet. Fabric samples are loaded
into a KENMORE automatic washer with a ballast load to give a total
dry load of 4 lb. (1.0 kg). A commercial detergent is added (AATCC
1993 Standard Reference Detergent WOB) and the washer is filled to
a high water level with warm water (105.degree. F.)(41.degree. C.).
The samples and ballast are washed a designated number of times (5
HW=5 washes, 10 HW=10 washes, etc.) using a 12-minute normal wash
cycle followed by rinse and spin cycles. The samples are not dried
between wash cycles.
[0064] After washing is complete, the wet fabric samples and
ballast are transferred to a KENMORE automatic dryer and dried for
45 minutes at the high/cotton setting to achieve a vent temperature
of 155-160.degree. F. (68-71.degree. C.).
EXAMPLES
[0065] The following materials are used in the Examples as
indicated.
[0066] ARMEEN DM-12D is N,N-dimethyidodecyl amine available from
Akzo Chemicals Inc., Chicago, Ill.
[0067] ARMEEN DM-18D is N,N-dimethyloctadecyl amine available from
Akzo Chemicals Inc., Chicago, Ill.
[0068] VAZO 56 WSP is an azo polymerization initiator
2,2'-azobis(2-amedinopropane)dihydrochloride available from E. I.
du Pont de Nemours and Company, Wilmington, Del.
[0069] ZONYL 7700, ZONYL 8315, ZONYL 8932 and ZONYL 8300 are each
fluorochemicals useful as treating agents for textiles available
from E. I. du Pont de Nemours and Company, Wilmington, Del.
Example 1
[0070] To begin, 70 g of 2-ethylhexylmethacrylate; 10 g of
poly(oxyethylene)7 methacrylate; 2 g of aqueous 48%
N-methylol-acrylamide; 0.3 g of dodecyl mercaptan, 20 g hexylene
glycol, 1.6 g of ARMEEN DM 18D, 1.0 g acetic acid, 3 g of aqueous
2% salt (NaCl) solution, and 80 g of hot (50-60.degree. C.)
deionized water were emulsified and then charged to a four-necked
flask fitted with a stirrer, thermocouple thermometer, and water
condenser. The charge was rinsed into the flask with 75 g of hot
deionized water and purged with nitrogen at 65.degree. C. for 30
minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I. du Pont de Nemours
and Company, Wilmington, Del.) dissolved in 2 g deionized water was
added to initiate polymerization. The temperature of the mix rose
spontaneously to 79.degree. C. over about 12 minutes, and then
began to decline. The temperature controller was reset to
70.degree. C., and the charge was stirred for 4 hours under
nitrogen. The resulting polymer extender latex (dispersion in
water) weighed 251 g with solids content of 31.7%. It was
separately blended with commercially available fluorochemicals,
ZONYL 7700, ZONYL 8315 and ZONYL 8932 from E. I. du Pont de Nemours
and Company, Wilmington, Del. in a ratio of 1:2 of fluorochemical
to extender.
[0071] The blend with ZONYL 7700 was applied to a 100%
polypropylene nonwoven substrate using the process of Test Method
1. A total of 32 g/L of the blended product was used in the pad
bath. The blended product contained 31% of ZONYL 7700 and 69% of
the non-fluorinated extender, which gave a blended product with
about 2.3% fluorine. About 5 g/L of a wetting agent (hexanol) was
used in the pad bath. About 2 g/L of an anti-stat, ZELEK KC,
available from Stepan, Northfield, Ill., was also used in the pad
bath. After application, the nonwoven fabrics were cured at about
100.degree. C. for about 4 minutes. The fabric was allowed to
"rest" after treatment and cure. The polypropylene nonwoven was
tested for water repellency using Test Method 2 described above.
ZONYL 7200 with no extender present was applied to the substrate in
the same manner for comparison. Results are in Table 3.
[0072] The blend with ZONYL 8315 was applied to a 100% polyester
nonwoven substrate using the fabric treatment process described
above in Test Method 1. 20 g/L of the blended product was used in
the pad bath. The blended products contained about 2.7% fluorine.
Approximately 15 g/L of a wax extender was used, FREEPEL 1225WR,
available from Omnova Solutions, Chester, S.C. After application,
the nonwoven fabrics were cured at about 170.degree. C. for about 2
minutes. The fabric was allowed to "rest" after treatment and cure.
The polyester nonwoven was tested for water repellency, spray
repellency, and impact repellency using Test Methods 2, 3 and 5 as
described above. ZONYL 8315 with no extender present was applied to
the substrate in the same manner for comparison. Results are listed
in Table 4.
[0073] The blend with ZONYL 8932 was applied to 100% nylon fabric
using Test Method 1 described above. The bath contained 45 g/L of
the blended product. The blended product contained about 3.5%
fluorine. For one sample, the bath contained between 0 and 1 g/L
blocked isocyanate. The blocked isocyanate used was HYDROPHOBOL
XAN, Ciba Specialty Chemicals, High Point, N.C. A wetting agent was
also included in the bath at 2 g/L. This was ALKANOL 6112 available
from E. I. du Pont de Nemours and Company, Wilmington, Del. After
application, the fabrics were cured at about 160.degree. C. for 3
minutes. The fabric was allowed to "rest" after treatment and cure.
The nylon was tested for oil repellency, water repellency and spray
repellency using Test Methods 4, 2 and 3 described above. ZONYL
8932 with no extender present was applied to the substrate in the
same manner for comparison. Results are listed in Table 5.
Example 2
[0074] The procedure of Example 1 was followed except that 4 g BRIJ
58 available from Uniqema, New Castle, Del., was also added before
emulsification. Yield was 252 g of polymer extender latex at 33.1%
solids which was blended with the fluorochemicals in a ratio of 1:2
of fluorochemical to extender, and applied to polypropylene and
polyester nonwovens as described in Example 1. The fabric was
tested as described in Example 1. Results are in Tables 3 and
4.
Comparative Example A
[0075] To begin, (a) 80 g of 2-ethylhexylmethacrylate; (c) 3.3 g of
aqueous 48% N-methylol-acrylamide; (e) 0.4 ethylene dimethacrylate;
1.6 g of ARMEEN DM 18D, 1.0 g acetic acid, 3 g of aqueous 2% salt
(NaCl) solution, and 135 g of warm (40-50.degree. C.) water were
emulsified and then charged to a four-necked flask fitted with a
stirrer, thermocouple thermometer, and a dry ice or water
condenser. The charge was rinsed into the flask with 20 g of cool
deionized water purged with nitrogen at 50.degree. C. for 30
minutes. Then the nitrogen was switched to a slow sweep, and 19 gm
of acetone was added. Then, 0.02 g of "VAZO" 56 WSP (E. I. du Pont
de Nemours and Company, Wilmington, Del.) was then added to
initiate polymerization. The temperature was ramped steadily up to
70.degree. C. over about 30 minutes. The temperature continued to
rise to 73.degree. C. over the next 10-12 minutes. The charge was
stirred for 3.5 hours at 70.degree. C. under nitrogen. The
resulting polymer latex weighed 244 g with solids content of 31.4%.
It was blended at a ratio of about 2:1 of extender to
fluorochemical with commercially available fluorochemicals as
listed in Table 5. The blend was applied to nylon fabric and tested
as in Example 1. Results are listed in Table 5.
Comparative Example B
[0076] To begin, (a) 80 g of 2-ethylhexylmethacrylate; (c) 3.3 g of
aqueous 48% N-methylol-acrylamide; 1.6 g of ARMEEN DM 18D, 1.0 g
acetic acid, 3 g of aqueous 2% salt (NaCl) solution, and 135 g of
warm (40-50.degree. C.) water were emulsified and then charged to a
four-necked flask fitted with a stirrer, thermocouple thermometer,
and a dry ice or water condenser. The charge was rinsed into the
flask with 20 g of cool deionized water purged with nitrogen at
50.degree. C. for 30 minutes. Then the nitrogen was switched to a
slow sweep, and 19 gm of acetone was added. Then, 0.02 g of "VAZO"
56 WSP (E. I. du Pont de Nemours and Company, Wilmington, Del.) was
then added to initiate polymerization. The temperature was ramped
steadily up to 70.degree. C. over about 30 minutes. The temperature
continued to rise to 73.degree. C. over the next 10-12 minutes. The
charge was stirred for 3.5 hours at 70.degree. C. under nitrogen.
The resulting polymer latex weighed 242 g with solids content of
31.2%. It was blended at a ratio of about 2:1 of extender to
fluorochemical with commercially available fluorochemicals as
listed in Tables 4 and 5. The blend was applied to a polyester
nonwoven substrate and a nylon fabric and tested as in Example 1.
Results are listed in Tables 4 and 5. TABLE-US-00003 TABLE 3
Polypropylene nonwoven Fluorochemical ZONYL 7700 ZONYL 7700 ZONYL
7700 Example Extender None 1 2 Water Repellency Initial 11 11 11
Spray Repellency Initial 90 90 90
[0077] Table 3 illustrates the efficacy of the extenders of the
present invention. The bath used to treat the nonwoven had 40% less
fluorochemical when the extender of Examples 1 and 2 were present
vs. no extender present, while the performance of the treatment was
maintained. TABLE-US-00004 TABLE 4 Polyester nonwoven ZONYL ZONYL
Fluorochemical 8315 8315 ZONYL 8315 ZONYL 8315 Example None 1 2
Comp. B Extender Water Repellency Initial 8 8 8 6 Spray Repellency
Initial 80 80 80 70 Impact Repellency Initial 0.32 0.1 0.1 0.3
GRAMS Standard 0.15474 0.16258 0.00577 0.00577 Deviation
[0078] Table 4 illustrates the efficacy of the extenders of the
present invention. The bath used to treat the nonwoven contained
25% less fluorochemical when the extenders of Examples 1 and 2 were
present vs. no extender present, while the performance of the
treatment was maintained. Further, the extenders of Examples 1 and
2 performed better at the same fluorine level than the extender of
Comparative Example B. TABLE-US-00005 TABLE 5 Nylon Fluorochemical
ZONYL ZONYL ZONYL ZONYL ZONYL 8932 8932 8932 8932 8932 Example None
Comp. A Comp. B 1 1 Extender Oil Repellency Note 1* Initial 6 5.5 6
6 5 5 HW** 3 2 2 6 4 10 HW** 2 1 0 5 2 Water Repellency Initial 11
10 10.5 12 10 5 HW** 8 5 4 11 7 10 HW** 4 4 3 9 4 Spray Repellency
Initial 100 90 90 100 100 5 HW** 50 50 50 75 80 10 HW** 50 50 50 70
50 *Note 1: A small amount of blocked isocyanate was added in this
Example. **5 HW = 5 washes; 10 HW = 10 washes
[0079] Table 5 illustrates the efficacy of the extenders of the
present invention. The bath used to treat the nylon contained a 50%
reduction of fluorochemical when the extender of Example 1 was used
vs. no extender present while the durability of performance of the
treatment was maintained. The extender of Example 1 performed
better at the same fluorine level when compared to the Comparative
Examples A and B. The performance of Example 1 and its durability
was excellent. The use of the blocked isocyanate improved the
repellency compared to Example 1 without it.
Example 3
[0080] To begin, (a) 60 g of 2-ethylhexylmethacrylate; (b) 10 g of
poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48%
N-methylol-acrylamide; (d) 10 g methyl methacrylate; 0.3 g of
dodecyl mercaptan, 20 g hexylene glycol, 1.6 g of ARMEEN DM 18D,
1.0 g acetic acid, 3 g of aqueous 2% salt (NaCl) solution, and 80 g
of hot (50-60.degree. C.) deionized water were emulsified and then
charged to a four-necked flask fitted with a stirrer, thermocouple
thermometer, and a water condenser. The charge was rinsed into the
flask with 75 g of hot deionized water and purged with nitrogen at
65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I.
du Pont de Nemours and Company, Wilmington, Del.) dissolved in 2 g
of deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 80.degree. C. and then began to
drop. The temperature controller was reset to 70.degree. C. and the
charge was stirred for 3.5 hours under nitrogen. The resulting
polymer extender latex weighed 255 g with solids content of 31.6%.
It was blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6 below,
and applied to 100% cotton fabric using the fabric treatment
process described above in Test Method 1. Generally 45 g/L of the
blended product was used in the pad bath. The blended products
contained between 2.2 and 3.5% fluorine. A blocked isocyanate was
used in the pad bath. The level of the isocyanate was between 5 and
10 g/L. An anti-wrinkle-resin was included at 60 g/L, PERMAFRESH
EFC available from Omnova Solutions, Chester, S.C. After
application, the fabrics were cured at about 160.degree. C. for 3
minutes. The fabric was allowed to "rest" after treatment and cure.
The fabric was tested for water repellency, oil repellency, and
spray repellency using Test Methods 2 to 5 described above. After
laundering in accordance with Test Method 6 described above, the
fabric was retested for water repellency, oil repellency, and spray
repellency using the same methods. Results are in Table 6.
Comparative Examples A and B were applied to 100% cotton fabric,
tested, laundered, and retested in the same manner as Example 3.
Results are also in Table 6. Comparative Examples A and B did not
enhance the durability of the fluorochemical as the extenders of
the present invention did.
Example 4
[0081] To begin, (a) 67 g of 2-ethylhexylmethacrylate; (b) 10 g of
poly(oxyethylene)7 methacrylate;(c) 2 g of aqueous 48%
N-methylol-acrylamide; (f) 3 g of ZONYL TM (E. I. du Pont de
Nemours and Company, Wilmington, Del.); 0.3 g of dodecyl mercaptan,
20 g hexylene glycol, 1.6 g of ARMEEN DM 18D, 1.0 g acetic acid, 3
g of aqueous 2% salt (NaCl) solution, and 80 g of hot
(50-60.degree. C.) deionized water were emulsified and then charged
to a four-necked flask fitted with a stirrer, thermocouple
thermometer, and a water condenser. The charge was rinsed into the
flask with 75 g of hot deionized water and purged with nitrogen at
65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I.
du Pont de Nemours and Company, Wilmington, Del.) dissolved in 2 g
of deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 77.degree. C. and then began to
drop. The temperature controller was reset to 70.degree. C. and the
charge was stirred for 3.5 hours under nitrogen. The resulting
polymer extender latex weighed 252 g with solids content of 31.6%.
It was blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6 below.
The blends were applied to 100% cotton fabric, laundered and
retested as described in Example 3. Results are in Table 6. The
inclusion of the fluorinated monomer in the extender did not appear
to increase the copolymer extender effectiveness.
Example 5
[0082] To begin, (a) 63 g of 2-ethylhexylmethacrylate; (b) 10 g of
poly(oxyethylene)7 methacrylate;(c) 2 g of aqueous 48% N
-methylol-acrylamide; (f) 7 g of ZONYL (E. I. du Pont de Nemours
and Company, Wilmington, Del.); 0.3 g of dodecyl mercaptan, 20 g
hexylene glycol, 1.6 g of ARMEEN DM 18D, 1.0 g acetic acid, 3 g of
aqueous 2% salt (NaCl) solution, and 80 g of hot (50-60.degree. C.)
deionized water were emulsified and then charged to a four-necked
flask fitted with a stirrer, thermocouple thermometer, and a water
condenser. The charge was rinsed into the flask with 75 g of hot
deionized water and purged with nitrogen at 65.degree. C. for 30
minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I. du Pont de Nemours
and Company, Wilmington, Del.) dissolved in 2 g of deionized water
was then added to initiate polymerization. Temperature rose
spontaneously to 78.degree. C. and then began to drop. The
temperature controller was reset to 70.degree. C. and the charge
was stirred for 3.5 hours under nitrogen. The resulting polymer
extender latex weighed 253 g with solids content of 31.5%. It was
blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6. The
blend was applied to 100% cotton fabric, tested, laundered, and
retested as in Example 3. Results are in Table 6. The inclusion of
the fluorinated monomer in the extender did not appear to increase
the copolymer extender effectiveness.
Example 6
[0083] To begin, (a) 70 g of 2-ethylhexylmethacrylate; (b) 10 g
poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48%
N-methylol-acrylamide; (e) 0.3 g ethylene dimethacrylate; 1.6 g of
ARMEEN DM 18D, 1.0 g acetic acid, 0.3 g of dodecyl mercaptan, 20 g
hexylene glycol, 3 g of aqueous 2% salt (NaCl) solution, and 80 g
of hot (50-60.degree. C.) deionized water were emulsified and then
charged to a four-necked flask fitted with a stirrer, thermocouple
thermometer, and a water condenser. The charge was rinsed into the
flask with 75 g of hot deionized water and purged with nitrogen at
65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I.
du Pont de Nemours and Company, Wilmington, Del.) dissolved in 2 g
of deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 79.degree. C. and then began to
drop. The temperature controller was reset to 70.degree. C. and the
charge was stirred for 3.5 hours under nitrogen. The resulting
polymer extender latex weighed 252 g with solids content of 32.2%.
It was blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6. The
blend was applied to 100% cotton fabric, tested, laundered, and
retested as in Example 3. Results are in Table 6.
Example 7
[0084] To begin, (a) 70 g of 2-ethylhexylmethacrylate; (b) 10 g
poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48%
N-methylol-acrylamide; (e) 0.5 g ethylene dimethacrylate; 1.6 g of
ARMEEN DM 18D, 1.0 g acetic acid, 0.3 g of dodecyl mercaptan, 20 g
hexylene glycol, 3 g of aqueous 2% salt (NaCl) solution, and 80 g
of hot (50-60.degree. C.) deionized water were emulsified and then
charged to a four-necked flask fitted with a stirrer, thermocouple
thermometer, and a water condenser. The charge was rinsed into the
flask with 75 g of hot deionized water and purged with nitrogen at
65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I.
du Pont de Nemours and Company, Wilmington, Del.) dissolved in 2 g
of deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 79.degree. C. over about 10
minutes and then began to drop. The temperature controller was
reset to 70.degree. C. and the charge was stirred for 3.5 hours
under nitrogen. The resulting polymer extender latex weighed 251 g
with solids content of 31.7%. It was blended at a ratio of 2:1 of
extender to fluorochemical with commercially available
fluorochemicals as listed in Table 6. The blend was applied to 100%
cotton fabric, tested, laundered, and retested as in Example 3.
Results are in Table 6.
Example 8
[0085] To begin, (a) 55 g of 2-ethylhexylmethacrylate; (b) 10 g of
poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48%
N-methylol-acrylamide; (d) 15 g steryl methacrylate; 0.3 g of
dodecyl mercaptan, 20 g hexylene glycol, 1.6 g of Armeen DM 18D,
1.0 g acetic acid, 3 g of aqueous 2% salt (NaCl) solution, and 80 g
of hot (50-60.degree. C.) deionized water were emulsified and then
charged to a four-necked flask fitted with a stirrer, thermocouple
thermometer, and a water condenser. The charge was rinsed into the
flask with 75 g of hot deionized water and purged with nitrogen at
65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I.
du Pont de Nemours and Company, Wilmington, Del.) dissolved in 2 g
of deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 77.degree. C. and then began to
drop. The temperature controller was reset to 70.degree. C. and the
charge was stirred for 3.5 hours under nitrogen. The resulting
polymer extender latex weighed 241 g with solids content of 31.3%.
It was blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6. The
blend was applied to 100% cotton fabric using the fabric, tested,
laundered, and retested as in Example 3. Results are in Table
6.
Example 9
[0086] To begin, (a) 70 g of 2-ethylhexylmethacrylate; (b) 7 g of
poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48%
N-methylol-acrylamide; 0.3 g of dodecyl mercaptan, 20 g hexylene
glycol, 1.6 g of ARMEEN DM 18D, 1.0 g acetic acid, 3 g of aqueous
2% salt (NaCl) solution, and 80 g of hot (50-60.degree. C.)
deionized water were emulsified and then charged to a four-necked
flask fitted with a stirrer, thermocouple thermometer, and water
condenser. The charge was rinsed into the flask with 75 g of hot
deionized water and purged with nitrogen at 65.degree. C. for 30
minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I. du Pont de Nemours
and Company, Wilmington, Del.) dissolved in 2 g deionized water was
then added to initiate polymerization. The temperature of the mix
rose spontaneously to 79.degree. C. over about 15 minutes, and then
began to decline. The temperature controller was reset to
70.degree. C., and the charge was stirred for 3.5 hours under
nitrogen. The resulting polymer extender latex weighed 249 g with
solids content of 30.7%. It was blended at a ratio of 2:1 of
extender to fluorochemical with commercially available
fluorochemicals as listed in Table 6. The blend was applied to 100%
cotton fabric, tested, laundered, and retested as in Example 3.
Results are in Table 6.
Example 10
[0087] To begin, (a) 70 g of 2-ethylhexylmethacrylate; (b) 10 g
poly(oxyethylene)7 methacrylate; 1.6 g of ARMEEN DM 18D, 1.0 g
acetic acid, 0.3 g of dodecyl mercaptan, 20 g hexylene glycol, 3 g
of aqueous 2% salt (NaCl) solution, and 80 g of hot (50-60.degree.
C.) deionized water were emulsified and then charged to a
four-necked flask fitted with a stirrer, thermocouple thermometer,
and a water condenser. The charge was rinsed into the flask with 75
g of hot deionized water and purged with nitrogen at 65.degree. C.
for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. I. du Pont de
Nemours and Company, Wilmington, Del.) dissolved in 2 g of
deionized water was then added to initiate polymerization.
Temperature rose spontaneously to 80.degree. C. and then began to
drop. The temperature controller was reset to 70.degree. C. and the
charge was stirred for 3.5 hours under nitrogen. The resulting
polymer extender latex weighed 251 g with solids content of 31.9%.
It was blended at a ratio of 2:1 of extender to fluorochemical with
commercially available fluorochemicals as listed in Table 6. The
blend was applied to 100% cotton fabric, tested, laundered, and
retested as in Example 3. Results are listed in Table 6.
Example 11
[0088] To begin, (a) 60 g of 2-ethylhexylmethacrylate; (b) 10 g of
poly(oxyethylene)7 methacrylate; (d) 10 g methyl methacrylate; 0.3
g of dodecyl mercaptan, 20 g hexylene glycol, 1.6 g of Armeen DM
18D, 1.0 g acetic acid, 3 g of aqueous 2% salt (NaCl) solution, and
80 g of hot (50-60.degree. C.) deionized water were emulsified and
then charged to a four-necked flask fitted with a stirrer,
thermocouple thermometer, and a water condenser. The charge was
rinsed into the flask with 75 g of hot di water and purged with
nitrogen at 65.degree. C. for 30 minutes. Then, 0.08 g of "VAZO" 56
WSP (E. I. du Pont de Nemours and Company, Wilmington, Del.)
dissolved in 2 g of deionized water was then added to initiate
polymerization. Temperature rose spontaneously to 78.degree. C. and
then began to drop. The temperature controller was reset to
70.degree. C. and the charge was stirred for 3.5 hours under
nitrogen. The resulting polymer extender latex weighed 258 g with
solids content of 31.3%. It was blended at a ratio of 2:1 of
extender to fluorochemical with commercially available
fluorochemicals as listed in Table 6. The blend was applied to 100%
cotton fabric, tested, laundered, and retested as in Example 3.
Results are listed in Table 6. TABLE-US-00006 TABLE 6 100% Cotton
Fluorochemical ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL
ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL 8932 8300 8932 8300 8932 8300
8932 8300 8932 8300 8932 8300 8932 8300 Example 1 1 A A B B 2 2 3 3
4 4 5 5 Extender Oil Repellency Initial 7 7 6 4 5 6 6+ 7 6+ 6 7 7 7
7 5 HW* 6 6 2 2 1 4 6 6 6 6 6 6 6 6 10 HW* 6 5 2 2 0 2 5 5 5 5 5 5
5 5 Water Repellency Initial 12 7 11 5 11 6 12 7 12 12 12 12 12 12
5 HW* 11 7 5 4 4 5 11 7 12 12 11 12 12 11 10 HW* 11 6 4 4 3 4 9 5 7
7 10 7 10 8 Spray Repellency Initial 100 100 90 90 100 100- 100 90
100- 100- 100 100 100 100 5 HW* 70 70- 50 50+ 50 50 70- 50 50+ 70
70- 50 70- 50+ 10 HW* 50 50 50 50 50 50 50 50/0 50 50 50 50 50 50
*5 HW = 5 washes; 10 HW = 10 washes Fluorochemical ZONYL ZONYL
ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL 8932 8300 8932 8300 8932 8932
8932 8932 Example Extender 6 6 7 7 8 9 10 11 Oil Repellency Initial
7 7 7 6 7 7 5+ 7 5 HW* 5 6 5 5 6 5 5+ 5 10 HW* 5 5 5 4 5 4 3 3 20
HW* 1 2 2 2 Water Repellency Initial 12 12 12 12 12 12 12 9+ 5 HW*
10 7 9 6 9 8 11 9 10 HW* 8 5 8 5 9 7 5 5 20 HW* 5 5 4 3 Spray
Repellency Initial 100 100- 100 100- 100 100 100 100 5 HW* 70- 50
50+ 50 50+ 70- 70+ 70 10 HW* 50 50 50 50 50 50 50+ 50 20 HW* 50 50
50 0 *5 HW = 5 washes; 10 HW = 10 washes; 20 HW = 20 washes
[0089] The durability of performance after washing the treated
fabrics the indicated number of times for the blends containing
extenders of Examples 1-11 was superior to the blends containing
Comparative Examples A and B when applied at the same fluorine
level, especially with reference to the oil and water drop
repellency.
Comparative Example C
[0090] To begin, 3 g of aqueous 2% salt (NaCl) solution, 4.2 g
hexylene glycol, 2 g of ARMEEN DM 18D, 6 g of ethoxylated tridecyl
alcohol (ETHAL TDA 5, available from Ethox Chemicals, Greenville,
S.C.) and 217 g of water were charged to a four-necked flask fitted
with a stirrer, thermocouple thermometer, and a water condenser.
The charge was purged with nitrogen at 65.degree. C. for 30
minutes. Then, 0.06 g of "VAZO" 56 WSP (E. I. du Pont de Nemours
and Company, Wilmington, DE) in 2 g water was then added. Then a
slow, steady, drop wise addition of a mixture of (b) 4 g of
poly(oxyethylene)7 methacrylate, (d) 76 g methyl methacrylate, and
0.8 g of dodecyl mercaptan, was begun. The monomer mixture was
added over about 80 minutes, with temperature maintained between 65
and 67.degree. C. Then the charge was stirred for 2.5 hours at
70.degree. C. under nitrogen. The resulting polymer latex weighed
309 g with solids content of 28%. It was blended at a ratio of 2:1
of extender to fluorochemical with ZONYL 8932 available from E. I.
du Pont de Nemours and Company. The blended products contained 3.5%
fluorine. The blend was applied to 100% cotton fabric using the
fabric treatment process described above in Test Method 1. 45 g/L
of the blended product was used in the pad bath. A blocked
isocyanate was also used in the pad bath. The level of the
isocyanate was between 5 and 10 g/L. An anti-wrinkle-resin was
included at 60 g/L, PERMAFRESH EFC available from Omnova Solutions,
Chester, S.C. After application, the fabrics were cured at about
160.degree. C. for 3 minutes. The fabric was allowed to "rest"
after treatment and cure. The fabric was tested for water
repellency, oil repellency, and spray repellency using Test Methods
2 to 4 described above. After laundering in accordance with Test
Method 6 described above, the fabric was retested for water
repellency, oil repellency, and spray repellency using the same
methods. Results are in Table 7.
Comparative Example D
[0091] To begin, 3 g of aqueous 2% salt (NaCl) solution, 4.2 g
hexylene glycol, 2 g of ARMEEN DM 18D, 6 g of ethoxylated tridecyl
alcohol (ETHAL TDA 5, available from Ethox Chemicals, Greenville,
S.C.) and 217 g of water were charged to a four-necked flask fitted
with a stirrer, thermocouple thermometer, and a water condenser.
The charge was purged with nitrogen at 65.degree. C. for 30
minutes. Then, 0.06 g of "VAZO" 56 WSP (E. I. du Pont de Nemours
and Company, Wilmington, Del.) in 2 g water was then added. Then a
slow, steady, drop wise addition of a mixture of (b) 4 g of
poly(oxyethylene)7 methacrylate, (d) 76 g methyl methacrylate, 2 g
of aqueous 48% N-methylol-acrylamide, and 0.8 g of dodecyl
mercaptan, was begun. The monomer mixture was added over about 80
minutes, with temperature maintained between 65 and 67.degree. C.
Then the charge was stirred for 2.5 hours at 70.degree. C. under
nitrogen. The resulting polymer latex weighed 311 g with solids
content of 28%. It was blended with ZONYL 8932 at a ratio of 2:1 of
extender to fluorochemical. The blend was applied to 100% cotton
fabric, tested, laundered, and retested as in Comparative Example
C. Results are in Table 7.
Comparative Example E
[0092] To begin, 3 g of aqueous 2% salt (NaCl) solution, 4.2 g
hexylene glycol, 2 g of ARMEEN DM 12D, 6 g of ethoxylated tridecyl
alcohol (ETHAL TDA 5, available from Ethox Chemicals, Greenville,
S.C.) and 217 g of water were charged to a four-necked flask fitted
with a stirrer, thermocouple thermometer, and a water condenser.
The charge was purged with nitrogen at 65.degree. C. for 30
minutes. Then, the nitrogen flow was switched to a slow sweep, and
0.05 g of potassium persulfate in 2 g water was added. Then a slow,
steady, drop wise addition of a mixture of (b) 4 g of
poly(oxyethylene)7 methacrylate, (d) 76 g methyl methacrylate, 0.3
g of dodecyl mercaptan, was begun. The monomer mixture was added
over about 90 minutes, with temperature maintained between 64 and
67 C. Then the charge was stirred for 2.5 hours at 70.degree. C.
under nitrogen. The resulting polymer latex weighed 307 g with
solids content of 27.6%. It was blended at a ratio of 2:1 of
extender to fluorochemical with ZONYL 8932. The blend was applied
to 100% cotton fabric, tested, laundered, and retested as in
Comparative Example C. Results are in Table 7. TABLE-US-00007 TABLE
7 100% Cotton ZONYL ZONYL ZONYL Fluorochemical 8932 8932 8932 ZONYL
8932 Extender Example 1 Comp. C Comp. D Comp. E Oil Repellency
Initial 7 5 5 6 5 HW* 6 3 4 4 10 HW* 6 2 2 2 Water Repellency
Initial 12 11 11 11 5 HW* 11 5 5 7 10 HW* 11 4 4 5 Spray Repellency
Initial 100 100- 100- 100- 5 HW* 70 70 70 70 10 HW* 50 70- 50 50 *5
HW = 5 washes; 10 HW = 10 washes
[0093] The durability after washing the treated fabric the
indicated number of times for performance of the blend containing
the extender of Example 1 is superior to the Comparative Examples,
C, D and E when applied at the same fluorine level, especially with
reference to the oil and water drop repellency.
Comparative Examples F and G
[0094] Comparative Examples F and G are the commercially available
extenders PHOBOTEX JVA available from Ciba Specialty Chemicals,
High Point, N.C. and FREEPEL 1225WR available from Omnova Solutions
Chester, S.C. These and the extender polymer of Example 1 were each
blended separately at a ratio of 2:1 of extender to fluorochemical
with ZONYL 8300 and ZONYL 8932, fluorochemicals available from E.
I. du Pont de Nemours and Company, Wilmington, DE. The blend was
applied to 100% cotton using the process of Test Method 1. 45 g/L
of the blended product was used in the pad bath. The blended
products contained between 2.2 and 3.5% fluorine. A blocked
isocyanate was also used in the pad bath. The level of the
isocyanate was between 5 and 10 g/L. An anti-wrinkle-resin was
included at 60 g/L, PERMAFRESH EFC available from Omnova Solutions,
Chester, S.C. After application, the fabrics were cured at about
160.degree. C. for 3 minutes. The fabric was allowed to "rest"
after treatment and cure. The fabric was tested, laundered, and
retested as in Example 3. Results are in Table 8. TABLE-US-00008
TABLE 8 100% Cotton Fluorochemical ZONYL ZONYL ZONYL ZONYL ZONYL
ZONYL 8932 8300 8932 8932 8300 8300 Example Extender 1 1 Comp. F
Comp. G Comp. F Comp. G Oil Repellency Initial 7 7 6 4 6 6 5 HW* 6
6 4 2 3 4 10 HW* 5 6 2 1 1 1 Water Repellency Initial 12 12 11 6 12
12 5 HW* 12 8 7 4 5 6 10 HW* 8 7 4 4 0 1 Spray Repellency Initial
100 100 100 70 90 100 5 HW* 70- 50 50 50 50 50 10 HW* 50 50 50 50
50/0 50/0 *5 HW = 5 washes; 10 HW = 10 washes
[0095] The durability of performance after washing the treated
fabric the indicated number of times for the blends containing the
commercial extenders (Comparative Examples F and G) are not
equivalent to the blends of the fluorochemical with the extenders
of the present invention (Example 1).
Example 12
[0096] The extender of Example 1 was blended with ZONYL 8932 in a
2:1 ratio of extender to ZONYL 8932, and with a blocked isocyanate
(1% on weight of bath (owb)) and a softener (1% owb). The blend
contained a ratio of ZONYL 8932 to extender to softener to blocked
isocyanate equal to 2:1:0.2:0.3. The blocked isocyanate used in
this case was HYDROPHOBOL XAN (Ciba Specialty Chemicals, High
Point, N.C.) and the softener used in this case was ARQUAD 2HT/75
(Akzo-Nobel, McCook, Ill.). This formulated product was applied to
100% cotton fabric at a level of 45 g/L in the pad bath using the
process of Test Method 1. An anti-wrinkle resin was included in the
pad bath at 60 g/L, PERMAFRESH EFC available from Omnova Solutions,
Chester, S.C. After application, the fabrics were cured at about
160.degree. C. for about 3 minutes. The fabric was allowed to
"rest" after treatment and cure. The fabric was tested for water
repellency, oil repellency, and spray repellency using Test Methods
2 to 4 described above. After laundering in accordance with Test
Method 6 described above, the fabric was retested for water
repellency, oil repellency, and spray repellency using the same
methods. Results are in Table 9.
Example 13
[0097] The extender of Example 1 was blended with ZONYL 8932 and
with a blocked isocyanate (1% owb) in a ratio of 3.6:1 of extender
to fluorochemical, to blocked isocyanate. This formulated product
was applied to 100% cotton fabric at a level of 30 g/L in the pad
bath using the process of Test Method 1. An anti-wrinkle resin was
included in the pad bath at 60 g/L, PERMAFRESH EFC available from
Omnova Solutions, Chester, S.C. After application, the fabrics were
cured at about 160.degree. C. for about 3 minutes. The fabric was
allowed to "rest" after treatment and cure. The fabric was tested
for water repellency, oil repellency, and spray repellency using
Test Methods 2 to 4 described above. After laundering in accordance
with Test Method 6 described above, the fabric was retested for
water repellency, oil repellency, and spray repellency using the
same methods. Results are in Table 9.
Example 14
[0098] The extender of Example 1 was blended with ZONYL 8932 and a
blocked isocyanate (1% owb) at a ratio of extender to
fluorochemical to blocked isocyanate of 2:1:0.3. This formulated
product was applied to 100% cotton fabric at a level of 45 g/L in
the pad bath using the process of Test Method 1. An anti-wrinkle
resin was included in the pad bath at 60 g/L, PERMAFRESH EFC
available from Omnova Solutions, Chester, S.C. After application,
the fabrics were cured at about 160.degree. C. for about 3 minutes.
The fabric was allowed to "rest" after treatment and cure. The
fabric was tested for water repellency, oil repellency, and spray
repellency using Test Methods 2 to 4 described above. After
laundering in accordance with Test Method 6 described above, the
fabric was retested for water repellency, oil repellency, and spray
repellency using the same methods. Results are in Table 9.
Example 15
[0099] The extender of Example 1 was blended with ZONYL 8932 and a
blocked isocyanate (1% owb) at a ratio of extender to
fluorochemical to blocked isocyanate of 3:1:0.3. This formulated
product was applied to 100% cotton fabric at a level of 30 g/L in
the pad bath using the process of Test Method 1. An anti-wrinkle
resin was included in the pad bath at 60 g/L, PERMAFRESH EFC
available from Omnova Solutions, Chester, S.C. After application,
the fabrics were cured at about 160.degree. C. for about 3 minutes.
The fabric was allowed to "rest" after treatment and cure. The
fabric was tested for water repellency, oil repellency, and spray
repellency using Test Methods 2 to 4 described above. After
laundering in accordance with Test Method 6 described above, the
fabric was retested for water repellency, oil repellency, and spray
repellency using the same methods. Results are in Table 9.
Example 16
[0100] The extender of Example 1 was blended with ZONYL 8932 and a
blocked isocyanate (1% owb) at a ratio of extender to
fluorochemical to blocked isocyanate of 6:1:0.3. This formulated
product was applied to 100% cotton fabric at a level of 30 g/L in
the pad bath using the process of Test Method 1. An anti-wrinkle
resin was included in the pad bath at 60 g/L, PERMAFRESH EFC
available from Omnova Solutions, Chester, S.C. After application,
the fabrics were cured at about 160.degree. C. for about 3 minutes.
The fabric was allowed to "rest" after treatment and cure. The
fabric was tested for water repellency, oil repellency, and spray
repellency using Test Methods 2 to 4 described above. After
laundering in accordance with Test Method 6 described above, the
fabric was retested for water repellency, oil repellency, and spray
repellency using the same methods. Results are in Table 9.
TABLE-US-00009 TABLE 9 100% Cotton Example ZONYL 8932 12 13 14 15
16 Oil Repellency Initial 6 7 6 7 6 2 5 HW* 5 6 4.5 6.5 5 1 10 HW*
3 5 2.5 5 3 1 20 HW* 1 3.5 2 4.5 1 0 Water Repellency Initial 12 12
12 12 12 5 5 HW* 7 11 8 11 6 4 10 HW* 5 10 5 11 4 3 20 HW* 3 4 4 7
4 3 Spray Repellency Initial 100 100 100 100 100 90 5 HW* 50 50 50
80 50 50 10 HW* 50 50 50 50+ 50 50 20 HW* 50 50 50 50 50 50 *5HW =
5 washes; 10 HW = 10 washes; 20 HW = 20 washes
[0101] The results show that the extender of the present invention
can be utilized in a number of formulations with and without
softeners and at various application levels. The fluorochemical
ZONYL 8932, when applied alone with no extender present, was
applied at a 30 g/L level in the pad bath using the same conditions
as Examples 12-16.
[0102] The data demonstrates that Examples 12-15 provide comparable
or superior durability of repellency with less percent fluorine
applied to the fabric. Example 16 had comparable spray repellency
with a reduction in fluorochemical of 6:1 compared to ZONYL 8932
alone.
* * * * *